Stable non-aqueous inkjet inks

ABSTRACT

A non-aqueous inkjet ink includes a diketopyrrolo-pyrrole pigment and at least one polyalkyleneglycol dialkylether having a molecular weight of at least 250. Also, a method for manufacturing decorative laminates using the non-aqueous inkjet ink is provided.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a 371 National Stage Application ofPCT/EP2007/054530, filed May 10, 2007. This application claims thebenefit of U.S. Provisional Application No. 60/809,496, filed May 31,2006, which is incorporated by reference herein in its entirety. Inaddition, this application claims the benefit of European ApplicationNo. 06114232.9, filed May 19, 2006, which is also incorporated byreference herein in its entirety.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to non-aqueous inkjet inks improved fordispersion stability and suitable for use in manufacturing decorativelaminates by single pass inkjet printing.

2. Description of the Related Art

Pigment dispersions are usually made using a dispersant. A dispersant isa substance for promoting the formation and stabilization of adispersion of pigment particles in a dispersion medium. Dispersants aregenerally surface-active materials having an anionic, cationic ornon-ionic structure. The presence of a dispersant substantially reducesthe dispersing energy required. Dispersed pigment particles may have atendency to re-agglomerate after the dispersing operation due to mutualattraction forces. The use of dispersants also counteracts thisre-agglomeration tendency of the pigment particles.

The dispersant has to meet particularly high requirements when used forinkjet inks. Inadequate dispersing manifests itself as increasedviscosity in liquid systems, loss of brilliance and/or hue shifts.Moreover, particularly good dispersion of the pigment particles isrequired to ensure unimpeded passage of the pigment particles throughthe nozzles of the print head, which are usually 10 to 50 micrometers indiameter. In addition, pigment particle agglomeration and the associatedblockage of the printer nozzles has to be avoided during the standbyperiods of the printer.

Polymeric dispersants generally contain in one part of the moleculeso-called anchor groups, which adsorb onto the pigments to be dispersed,and in a spatially separate part of the molecule, the polymericdispersants have polymer chains compatible with the dispersion medium,thus stabilizing the pigment particles in the dispersion medium. Typicalpolymeric dispersants include graft copolymer and block copolymerdispersants.

In aqueous inkjet inks, the polymeric dispersants generally containhydrophobic anchor groups exhibiting a high affinity for the pigmentsurface and hydrophilic polymer chains for stabilizing the pigments inthe aqueous dispersion medium.

The preparation of good thermally stable dispersions with submicronparticles is much more difficult for non-aqueous inkjet inks, such assolvent based, oil based and radiation curable inkjet inks. The pigmentsare especially difficult to disperse when they have a non-polar surface.

These dispersing problems have lead to the design of very specificpolymeric dispersants wherein the anchor groups are pigment derivatives.For example, EP 0763378 A (TOYO INK) discloses a pigment compositionincluding a non-aqueous type pigment dispersing agent having a portionwhich has a high affinity with a pigment and which has at least one typeselected from the group consisting of an organic dye, anthraquinone andacridone only at a terminal end or at both terminal ends of at least onepolymer selected from a linear urethane polymer and a linear acrylicpolymer, and a pigment.

Another approach for dispersing pigments with non-polar surfaces innon-aqueous dispersion media is changing the surface to a more polarsurface by addition of compounds known as dispersion synergists. Adispersion synergist is a compound that promotes the adsorption of thepolymeric dispersant on the surface of the pigment. It is suggested thatthe synergist should possess the pigment structure substituted by one ormore sulfonic acid groups or ammonium salts thereof.

U.S. Pat. No. 4,461,647 (ICI) discloses a dispersion of a pigment in anorganic liquid containing a water-insoluble asymmetric disazo compoundincluding a central divalent group free from acidic and other ionicsubstituents linked through azo groups to two monovalent end groupscharacterized in that one end group, the first, is free from acidic andother ionic substituents and the other end group, the second, carries asingle substituted ammonium-acid salt group.

Although these dispersion synergists work fine for some pigments, manyother pigments cannot be dispersed to an acceptable quality in anon-aqueous medium. This is, for example, the case fordiketopyrrolo-pyrrole pigments, for which it is difficult to obtainstable non-aqueous pigment dispersions, especially stable non-aqueousinkjet inks.

U.S. 2004/0122130 (CHANG ET AL.) discloses a photo-curable pigment typeinkjet ink composition containing Pigment Red 254, but the ink requiresthe presence of water and a reactive surfactant.

The dispersion quality and stability can also be influenced by thecomposition of the dispersion medium, however this also influences thebehavior of inkjet droplets jetted upon the ink-receiver surface.

Many types of solvents and specific combinations of solvents have beendisclosed. EP 1528086 A (SEIKO EPSON) discloses an oil-based inkjet inkincluding at least 50% of a mixed solvent of a lactone-type solvent anda polyoxyethyleneglycol dialkyl ether. It was discovered by the presentinventor that further improvements in dispersion stability and jettingcharacteristics, such as latency, were particularly required for singlepass inkjet printing. For certain inkjet applications, it would also bedesirable to make inks lacking a noxious solvent such as lactone.

For consistent image quality, inkjet inks require high dispersionstability capable of dealing with high temperatures (above 65° C.)during transport of the ink to a customer, jetting at elevatedtemperatures and changes in the dispersion medium of the inkjet inkduring use. These changes in the dispersion medium can occur, forexample, by evaporation of solvent and increasing concentrations ofhumectants, penetrants and other additives at the nozzles during thesummer or when the printer is not jetting ink for a long time (i.e.,latency) and the inkjet print-heads are filled with ink, e.g., over theweekend.

Inkjet printing provides large flexibility in the production ofdecorative laminates, but high printing speed is required to obtainacceptable productivity. This is possible with single pass inkjetprinting if the inkjet printing process is so reliable that during aprint job no maintenance is required. Inkjet inks having very highdispersion quality and stability and exhibiting minimal latency problemsare therefore required. Aqueous inkjet inks generally exhibit latencyproblems due to the relative high volatility of water.Diketopyrrolo-pyrrole pigments have been a preferred choice innon-inkjet printing inks, such as, e.g., gravure inks, to print imageson a decorative paper used in the manufacturing process of decorativelaminates for imitating a wooden floor. These pigments have beendispersed to acceptable dispersion quality and stability in aqueousinkjet inks but not in non-aqueous inkjet inks.

SUMMARY OF THE INVENTION

In order to overcome the problems described above, preferred embodimentsof the present invention are capable of manufacturing inkjet inksexhibiting high dispersion quality and stability while exhibitingminimal latency problems.

Another preferred embodiment of the present invention provides an inkjetink set for producing decorative laminates with a warm wooden colorappearance.

Further advantages and benefits achieved by preferred embodiments of thepresent invention will become apparent from the description hereinafter.

Surprisingly, it has been discovered that a reliable non-aqueous singlepass inkjet printing step could be integrated into the manufacturingprocess of decorative laminates capable of delivering decorativelaminates with a warm wooden color when non-aqueous pigmented inkjetinks including specific polyalkyleneglycol dialkylethers were used.

According to a preferred embodiment of the present invention, anon-aqueous inkjet ink includes a diketopyrrolo-pyrrole pigment and atleast one polyalkyleneglycol dialkylether having a molecular weight ofat least 250.

According to another preferred embodiment of the present invention, amethod for manufacturing decorative laminates includes the steps of a)providing a decorative paper; b) inkjet printing on the decorative paperwith a non-aqueous inkjet ink including C.I. Pigment Red 254; and c)impregnating the printed decorative paper with an impregnating resin.

The non-aqueous inkjet inks exhibit excellent latency so that no cappingof the print heads was required.

It was discovered that not only the diketopyrrolo-pyrrole pigments couldbe dispersed to an excellent quality and stability, but also a widerange of other pigments could be dispersed in non-aqueous inkjet inksexhibiting high dispersion quality and stability.

The non-aqueous inkjet inks did not require the presence of a surfactantfor printing images of high quality on decorative base paper.

These and other elements, characteristics, features, steps andadvantages of the present invention will become more apparent anddescribed in more detail in the following detailed description ofpreferred embodiments thereof.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Definitions

The term “colorant”, as used in the preferred embodiments of the presentinvention means dyes and pigments.

The term “dye”, as used in the preferred embodiments of the presentinvention means a colorant having a solubility of 10 mg/L or more in themedium in which it is applied and under the ambient conditionspertaining thereto.

The term “pigment” is defined in DIN 55943, herein incorporated byreference, as a coloring agent that is practically insoluble in theapplication medium under the pertaining ambient conditions, hence havinga solubility of less than 10 mg/L therein.

The term “C.I.” is used in the preferred embodiments of the presentapplication as an abbreviation for Colour Index.

The term “alkyl” means all variants possible for each number of carbonatoms in the alkyl group, i.e., for three carbon atoms: n-propyl andisopropyl; for four carbon atoms: n-butyl, isobutyl and tertiary-butyl;for five carbon atoms: n-pentyl, 1,1-dimethyl-propyl, 2,2-dimethylpropyland 2-methyl-butyl etc.

Non-aqueous Inkjet Inks

The non-aqueous inkjet inks according to preferred embodiments of thepresent invention include a pigment and at least one polyalkyleneglycoldialkylether having a molecular weight of at least 250.

In a preferred embodiment, the non-aqueous inkjet ink includes apolyalkyleneglycol dialkylether represented by Formula (I):

wherein,

R₁ and R₂ are each independently selected from an alkyl group having 1to 4 carbon atoms;

Y represents an ethylene group or a propylene group; and

n is an integer selected from 5 to 20. The alkylgroups R₁ and R₂ of thepolyalkyleneglycol dialkylethers according to Formula (I) preferablyrepresent methyl and/or ethyl. Most preferably, the alkylgroups R₁ andR₂ are both methyl groups.

In a preferred embodiment, the polyalkyleneglycol dialkylethersaccording to Formula (I) are polyethyleneglycol dialkylethers.

In another preferred embodiment, the non-aqueous inkjet ink includes asecond polyalkyleneglycol dialkylether according to Formula (I) havingthe integer n selected from 4 to 20, more preferably the integer n isselected from 6 to 17.

In another preferred embodiment, the non-aqueous ink includes apolyalkyleneglycol dialkylether represented by Formula (I) wherein theinteger n is equal to 6.

Suitable mixtures of polyalkyleneglycol dialkylethers for the pigmentdispersions according to preferred embodiments of the present inventioninclude mixtures of polyethylene glycol dimethyl ethers having amolecular weight of at least 200, such as Polyglycol DME ₂₀₀™,Polyglycol DME 250™ and Polyglycol DME 500™ from CLARIANT. Thepolyalkyleneglycol dialkylethers used in the non-aqueous inkjet inkpreferably have an average molecular weight between 200 and 800, andmore preferably no polyalkyleneglycol dialkylethers with a molecularweight of more than 800 are present. The mixture of polyalkyleneglycoldialkylethers is preferably a homogeneous liquid mixture at roomtemperature.

In another preferred embodiment, a mixture of 3 or morepolyalkyleneglycol dialkylethers, more preferably polyethyleglycoldialkylethers are present in the non-aqueous inkjet ink.

In another preferred embodiment, a non-aqueous inkjet ink includes apigment and a mixture of at least two polyalkyleneglycol dialkylethershaving four or more alkyleneglycol groups but the number ofalkyleneglycol groups is not the same in the two polyalkyleneglycoldialkylethers.

A non-aqueous inkjet ink is generally prepared in a two step process byfirst dispersing pigment and dispersant in one or more ‘dispersionsolvents’ to obtain a concentrated pigment dispersion and then dilutingthe pigment dispersion with one or more ‘ink solvents’ and othercomponents to obtain the desired viscosity, surface tension, color, hue,saturation density, and print area coverage for a particularapplication.

In a preferred embodiment, the dispersion solvent may be other organicsolvents than the polyalkyleneglycol dialkylether having a molecularweight of at least 250 which is included as the ink solvent.

In a preferred embodiment, the dispersion solvent includes thepolyalkyleneglycol dialkylether having a molecular weight of at least250, and the one or more organic solvents used as ink solvents can beother organic solvents but may include polyalkyleneglycol dialkylethers.

In another preferred embodiment, the non-aqueous inkjet ink furtherincludes a polyalkyleneglycol derivative selected from the groupconsisting of polyalkyleneglycol monoalkyl ether acetates andpolyalkyleneglycol monoalkyl ethers. In a preferred embodiment, thepolyalkyleneglycol derivative is selected from the group consisting ofdipropyleneglycol monomethyl ether acetate, diethyleneglycol monobutylether acetate, triethyleneglycol monobutyl ether and tripropyleneglycolmonomethylether.

The polyalkyleneglycol dialkylether having a molecular weight of atleast 250 is preferably present in the non-aqueous inkjet ink in aconcentration between 4 wt % and 98 wt %, more preferably between 15 wt% and 95 wt % and most preferably between 23 wt % and 90 wt % all basedupon the total weight of the non-aqueous inkjet ink.

The non-aqueous inkjet ink according to a preferred embodiment of thepresent invention may further contain at least one surfactant.

The non-aqueous inkjet ink according to a preferred embodiment of thepresent invention may contain at least one humectant to prevent theclogging of the nozzle due to its ability to slow down the evaporationrate of ink.

The non-aqueous inkjet ink according to a preferred embodiment of thepresent invention is preferably an organic solvent based inkjet ink, butmay also be a curable pigmented inkjet ink. The curable pigmented inkjetink is preferably radiation curable. The viscosity of the pigmentedinkjet ink is preferably lower than 100 mPa·s at 30° C. The viscosity ofthe pigmented inkjet ink is preferably lower than 30 mPa·s, morepreferably lower than 15 mPa·s, and most preferably between 2 and 10mPa·s all measured at a shear rate of 100 s⁻¹ and a jetting temperaturebetween 10 and 70° C.

The curable pigmented inkjet ink may contain as the dispersion mediummonomers, oligomers and/or prepolymers possessing different degrees offunctionality. A mixture including combinations of mono-, di-, tri-and/or higher functionality monomers, oligomers or prepolymers may beused. A catalyst called an initiator for initiating the polymerizationreaction may be included in the curable pigmented inkjet ink. Theinitiator can be a thermal initiator, but is preferably aphoto-initiator. The photo-initiator requires less energy to activatethan the monomers, oligomers and/or prepolymers to form the polymer. Thephoto-initiator suitable for use in the curable pigment dispersion maybe a Norrish type I initiator, a Norrish type II initiator or aphoto-acid generator.

For producing color images, the non-aqueous inkjet inks may be used inan inkjet ink set. Preferably, the inkjet ink set includes at least twonon-aqueous inkjet inks according to a preferred embodiment of thepresent invention. In a preferred embodiment, the inkjet ink setincludes at least a cyan ink, a magenta ink, a yellow ink and a blackink. The CMYK ink set may also be extended with extra inks such as red,green, blue, and/or orange to enlarge the color gamut of the image. TheCMYK ink set may also be extended by the combination of full density andlight density inks of both color inks and/or black inks to improve theimage quality by lowered graininess.

In a preferred embodiment, the inkjet ink set includes a non-aqueousinkjet ink having C.I. Pigment Red 254 as a pigment.

Preparation of Pigment Dispersions

The non-aqueous inkjet ink according to a preferred embodiment of thepresent invention may be prepared by milling the pigment in thedispersion medium, preferably in the presence of a polymeric dispersant.

Mixing apparatuses may include a pressure kneader, an open kneader, aplanetary mixer, a dissolver, and a Dalton Universal Mixer. Suitablemilling and dispersion apparatuses are a ball mill, a pearl mill, acolloid mill, a high-speed disperser, double rollers, a bead mill, apaint conditioner, and triple rollers. The dispersions may also beprepared using ultrasonic energy.

Many different types of materials may be used as milling media, such asglasses, ceramics, metals, and plastics. In a preferred embodiment, thegrinding media can include particles, preferably substantially sphericalin shape, e.g., beads consisting essentially of a polymeric resin oryttrium stabilized zirconium oxide beads.

In the process of mixing, milling and dispersion, each process isperformed with cooling to prevent the build up of heat, and forradiation curable inkjet inks as much as possible under light conditionsin which actinic radiation has been substantially excluded.

The non-aqueous inkjet ink according to a preferred embodiment of thepresent invention may contain more than one pigment, the non-aqueousinkjet ink may be prepared using separate dispersions for each pigment,or alternatively several pigments may be mixed and co-milled inpreparing the dispersion.

The dispersion process can be carried out in a continuous, batch orsemi-batch mode.

The preferred amounts and ratios of the ingredients of the mill grindwill vary widely depending upon the specific materials and the intendedapplications. The contents of the milling mixture include the mill grindand the milling media. The mill grind includes pigment, polymericdispersant and a liquid carrier. For inkjet inks, the pigment is usuallypresent in the mill grind at 1 to 50 wt %, excluding the milling media.The weight ratio of pigment over polymeric dispersant is 20:1 to 1:2.

The milling time can vary widely and depends upon the pigment, theselected mechanical devices and residence conditions, the initial anddesired final particle size, etc. In a preferred embodiment of thepresent invention, pigment dispersions with an average particle size ofless than 150 nm may be prepared.

After milling is completed, the milling media is separated from themilled particulate product (in either a dry or liquid dispersion form)using conventional separation techniques, such as by filtration, sievingthrough a mesh screen, and the like. Often the sieve is built into themill, e.g., for a bead mill. The milled pigment concentrate ispreferably separated from the milling media by filtration.

In general, it is desirable to make the inkjet inks in the form of aconcentrated mill grind, which is subsequently diluted to theappropriate concentration for use in the inkjet printing system. Thistechnique permits preparation of a greater quantity of pigmented inkfrom the equipment. By dilution, the inkjet ink is adjusted to thedesired viscosity, surface tension, color, hue, saturation density, andprint area coverage for the particular application.

In preparing the inkjet ink, it is preferred that one or more degassingsteps are performed at one time or another for removing air or gasbubbles from the ink. Degassing is preferably performed by heatingand/or reduced pressure. The degassing step(s) can be performed on theconcentrated pigment dispersion and/or on the final inkjet inkcomposition.

Pigments

The pigments used in the non-aqueous inkjet ink according to a preferredembodiment of the present invention may be black, white, cyan, magenta,yellow, red, orange, violet, blue, green, brown, mixtures thereof, andthe like.

The color pigment may be chosen from those disclosed by HERBST, Willy,et al., Industrial Organic Pigments, Production, Properties,Applications, 3rd Edition, Wiley—VCH, 2004, ISBN 3527305769.

Particularly preferred pigments are C.I. Pigment Yellow 1, 3, 10, 12,13, 14, 17, 55, 65, 73, 74, 75, 83, 93, 97, 109, 111, 120, 128, 138,139, 150, 151, 154, 155, 180,185 and 213.

Particularly preferred pigments are C.I. Pigment Yellow 120, 151, 154,175, 180, 181 and 194.

The most preferred yellow pigments are C.I. Pigment Yellow 120, 139, 150and 155.

Particularly preferred pigments are C.I. Pigment Red 17, 22, 23, 41,48:1, 48:2, 49:1, 49:2, 52:1, 57:1, 81:1, 81:3, 88, 112, 122, 144, 146,149, 169,170, 175, 176, 184, 185, 188, 202, 206, 207, 210, 216, 221,248, 251, 254, 255, 264, 270 and 272. For manufacturing decorativelaminates, the most preferred are C.I. Pigment Red 254 and C.I. PigmentRed 266. For other non-aqueous inkjet applications, the most preferredpigments are C.I. Pigment Red 122 and C.I. Pigment Violet 19.

Particularly preferred pigments are C.I. Pigment Violet 1, 2, 19, 23,32, 37 and 39.

Particularly preferred pigments are C.I. Pigment Blue 15:1, 15:2, 15:3,15:4, 15:6, 16, 56, 61 and (bridged) aluminum phthalocyanine pigments.

Particularly preferred pigments are C.I. Pigment Orange 5, 13, 16, 34,40, 43, 59, 66, 67, 69, 71 and 73.

Particularly preferred pigments are C.I. Pigment Green 7 and 36.

Particularly preferred pigments are C.I. Pigment Brown 6 and 7.

Suitable pigments include mixed crystals of the above particularlypreferred pigments. A commercially available example is CinquasiaMagenta RT-355-D from Ciba Specialty Chemicals.

Carbon black is preferred as a pigment for the non-aqueous black inkjetink because it always exhibits a warm brownish black tone.

Suitable black pigment materials include carbon blacks such as C.I.Pigment Black 7 (e.g. Carbon Black MA8® from MITSUBISHI CHEMICAL),Regal® 400R, Mogul® L, Elftex® 320 from CABOT Co., or Carbon Black FW18,Special Black 250, Special Black 350, Special Black 550, Printex® 25,Printex® 35, Printex® 55, Printex® 90, Printex® 150T from DEGUSSA.Additional examples of suitable pigments are disclosed in U.S. Pat. No.5,389,133 (XEROX). In a preferred embodiment, the C.I. Pigment Black 7has a BET surface area smaller than 200 m²/g measured according to ASTMD6556-04 Standard Test Method for Carbon Black-Total and ExternalSurface Area by Nitrogen Adsorption.

It is also possible to make mixtures of pigments in one pigmentdispersion or non-aqueous inkjet ink. For other applications thanmanufacturing decorative laminates, a neutral black inkjet ink isgenerally preferred and can be obtained, for example, by mixing a blackpigment and a cyan pigment into the ink. The inkjet application may alsorequire one or more spot colors, for example for packaging inkjetprinting or textile inkjet printing. Silver and gold are often desiredcolors for inkjet poster printing and point-of-sales displays.

Also, non-organic pigments can be advantageously dispersed according toa preferred embodiment of the present invention. Particularly preferredpigments are C.I. Pigment Metal 1, 2 and 3. Illustrative examples of theinorganic pigments include titanium oxide, barium sulfate, calciumcarbonate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red ironoxide (III), cadmium red, ultramarine blue, prussian blue, chromiumoxide green, cobalt green, amber, titanium black and synthetic ironblack.

Generally, pigments are stabilized in the dispersion medium bydispersing agents, such as polymeric dispersants or surfactants.However, the surface of the pigments can be modified to obtain so-called“self-dispersible” or “self-dispersing” pigments, i.e., pigments thatare dispersible in the dispersion medium without dispersants.

Pigment particles in the non-aqueous inkjet ink should be sufficientlysmall to permit free flow of the ink through the inkjet printing device,especially at the ejecting nozzles. It is also desirable to use smallparticles for maximum color strength and to slow down sedimentation.

The average particle size of the pigment in the pigmented inkjet inkshould be between 0.005 and 15 μm. Preferably, the average pigmentparticle size is between 0.005 and 5 μm, more preferably between 0.005and 1 μm, particularly preferably between 0.005 and 0.3 μm and mostpreferably between 0.040 and 0.150 μm. Larger pigment particle sizes maybe used as long as the advantages and benefits of the preferredembodiments of the present invention are achieved.

The pigment is preferably used in the non-aqueous pigment dispersionused for preparing the inkjet ink in an amount of 10 to 40 wt %,preferably 20 to 30 wt % based on the total weight of the pigmentdispersion. In the inkjet ink, the pigment is preferably used in anamount of 0.1 to 20 wt %, preferably 1 to 10 wt % based on the totalweight of the inkjet ink.

Dispersants

The non-aqueous inkjet ink according to a preferred embodiment of thepresent invention contains at least two components: (i) a pigment, and(ii) a liquid dispersion medium. If the pigment is not aself-dispersible pigment, the non-aqueous inkjet ink preferably containsa polymeric dispersant.

Typical polymeric dispersants are copolymers of two monomers but maycontain three, four, five or even more monomers. The properties ofpolymeric dispersants depend on both the nature of the monomers andtheir distribution in the polymer. Copolymeric dispersants suitable inpigment dispersions according to a preferred embodiment of the presentinvention may have the following polymer compositions:

-   -   randomly polymerized monomers (e.g., monomers A and B        polymerized into ABBAABAB);    -   alternating polymerized monomers (e.g., monomers A and B        polymerized into ABABABAB);    -   gradient (tapered) polymerized monomers (e.g., monomers A and B        polymerized into AAABAABBABBB);    -   block copolymers (e.g., monomers A and B polymerized into        AAAAABBBBBB) wherein the block length of each of the blocks (2,        3, 4, 5 or even more) is important for the dispersion capability        of the polymeric dispersant;    -   graft copolymers (graft copolymers consisting of a polymeric        backbone with side chains attached to the backbone); and    -   mixed forms of these polymers, e.g., blocky gradient copolymers.

Polymeric dispersants suitable in pigment dispersions according to apreferred embodiment of the present invention may have different polymerarchitectures including linear, comb/branched, star, dendritic(including dendrimers and hyperbranched polymers). A general review onthe architecture of polymers is given by ODIAN, George, Principles OfPolymerization, 4th Edition, Wiley-Interscience, 2004, pp. 1-18.

Comb/branched polymers have side branches of linked monomer moleculesprotruding from various central branch points along the main polymerchain (at least 3 branch points).

Star polymers are branched polymers in which three or more eithersimilar or different linear homopolymers or copolymers are linkedtogether to a single core.

Dendritic polymers include the classes of dendrimers and hyperbranchedpolymers. In dendrimers, with well-defined mono-disperse structures, allbranch points are used (multi-step synthesis), while hyperbranchedpolymers have a plurality of branch points and multifunctional branchesthat lead to further branching with polymer growth (one-steppolymerization process).

Polymeric dispersants suitable in pigment dispersions according to apreferred embodiment of the present invention may be prepared viaaddition or condensation type polymerizations. Polymerization methodsinclude those described by ODIAN, George, Principles of Polymerization,4th Edition, Wiley-Interscience, 2004, pp. 39-606.

Addition polymerization methods suitable for preparing polymericdispersants for use in pigment dispersions according to a preferredembodiment of the present invention include free radical polymerization(FRP) and controlled polymerization techniques. Suitable controlledradical polymerization methods include:

-   -   RAFT: reversible addition-fragmentation chain transfer;    -   ATRP: atom transfer radical polymerization    -   MADIX: reversible addition-fragmentation chain transfer process,        using a transfer active xanthate;    -   Catalytic chain transfer (e.g., using cobalt complexes);    -   Nitroxide (e.g., TEMPO) mediated polymerizations;

Other suitable controlled polymerization methods include:

-   -   GTP: group transfer polymerization;    -   Living cationic (ring-opening) polymerizations;    -   Anionic co-ordination insertion ring-opening polymerization; and    -   Living anionic (ring-opening) polymerization.

Reversible addition-fragmentation transfer (RAFT): controlledpolymerization occurs via rapid chain transfer between growing polymerradicals and dormant polymer chains. A review article on RAFT synthesisof dispersants with different polymeric geometry is given in QUINN, J.F. et al., Facile Synthesis of Comb, Star, and Graft Polymers viaReversible Addition-fragmentation Chain Transfer (RAFT) Polymerization,Journal of Polymer Science, Part A: Polymer Chemistry, Vol. 40, pp.2956-2966, 2002.

Group transfer polymerization (GTP): the method of GTP used forsynthesis of AB block copolymers is disclosed by SPINELLI, Harry J., GTPand its Use in Water Based Pigment Dispersants and Emulsion Stabilisers,Proc. of 20th Int. Conf. Org. Coat. Sci. Technol., New Platz, N.Y.,State Univ. N.Y., Inst. Mater. Sci., pp. 511-518.

The synthesis of dendritic polymers is described in the literature. Thesynthesis of dendrimers in NEWCOME, G. R. et al., Dendritic Molecules:Concepts, Synthesis, Perspectives, VCH: WEINHEIM, 2001. Hyperbranchingpolymerization is described by BURCHARD, W., Solution Properties ofBranched Macromolecules, Advances in Polymer Science, 1999, Vol. 143,No. II, pp. 113-194. Hyperbranched materials can be obtained bypolyfunctional polycondensation as disclosed by FLORY, P. J., MolecularSize Distribution in Three-dimensional Polymers. VI. Branched PolymerContaining A-R-Bf-1-type Units, Journal of the American ChemicalSociety, 1952, Vol. 74, pp. 2718-2723.

Living cationic polymerizations is, e.g., used for the synthesis ofpolyvinyl ethers as disclosed in WO 2005/012444 (CANON) and U.S.2005/0197424 (CANON). Anionic co-ordination ring-opening polymerizationis, e.g., used for the synthesis of polyesters based on lactones. Livinganionic ring-opening polymerization is, e.g., used for the synthesis ofpolyethylene oxide macromonomers.

Free radical Polymerization (FRP) proceeds via a chain mechanism, whichbasically consists of four different types of reactions involving freeradicals: (1) radical generation from non-radical species (initiation),(2) radical addition to a substituted alkene (propagation), (3) atomtransfer and atom abstraction reactions (chain transfer and terminationby disproportionation), and (4) radical-radical recombination reactions(termination by combination).

Polymeric dispersants having several of the above polymer compositionsare disclosed in U.S. Pat. No. 6,022,908 (HEWLETT-PACKARD COMPANY), U.S.Pat. No. 5,302,197 (DU PONT) and U.S. Pat. No. 6,528,557 (XEROXCORPORATION).

Suitable random copolymeric dispersants are disclosed in U.S. Pat. No.5,648,405 (DU PONT), U.S. Pat. No. 6,245,832 (FUJI XEROX), U.S. (3MINNOVATIVE PROPERTIES COMPANY), U.S. 2005/0004262 (KAO CORPORATION) andU.S. Pat. No. 6,852,777 B1 (KAO CORPORATION).

Suitable alternating copolymeric dispersants are described in U.S.2003/0017271 (AKZO NOBEL N.V.).

Suitable block copolymeric dispersants have been described in numerouspatents, especially block copolymeric dispersants containing hydrophobicand hydrophilic blocks. For example, U.S. Pat. No. 5,859,113 (DU PONT)discloses AB block copolymers, U.S. Pat. No. 6,413,306 (DU PONT)discloses ABC block copolymers.

Suitable graft copolymeric dispersants are described in CA 2157361 (DUPONT) (hydrophobic polymeric backbone and hydrophilic side chains);other graft copolymeric dispersants are disclosed in U.S. Pat. No.6,652,634 (LEXMARK), U.S. Pat. No. 6,521,715 (DU PONT) and U.S.2004/0102541 (LEXMARK).

Suitable branched copolymeric dispersants are described in U.S. Pat. No.6,005,023 (DU PONT), U.S. Pat. No. 6,031,019 (KAO CORPORATION), U.S.Pat. No. 6,127,453 (EASTMAN KODAK).

Suitable dendritic copolymeric dispersants are described in, e.g., U.S.Pat. No. 6,518,370 (3M INNOVATIVE PROPERTIES COMPANY), U.S. Pat. No.6,258,896 (3M INNOVATIVE PROPERTIES COMPANY), WO 2000/063305 (GEMGRAVURE CORPORATION), U.S. Pat. No. 6,649,138 (QUANTUM DOT CORPORATION),U.S. 2002/0256230 (BASF), EP 1351759 (EFKA ADDITIVES), and EP 1295919(EASTMAN KODAK).

Suitable designs of polymeric dispersants for inkjet inks are disclosedin SPINELLI, Harry J., Polymeric Dispersants in Ink Jet technology,Advanced Materials, 1998, Vol. 10, No. 15, pp. 1215-1218.

The monomers and/or oligomers used to prepare the polymeric dispersantcan be any monomer and/or oligomer found in the Polymer Handbook Vol1+2, 4th Edition, edited by J. BRANDRUP et al., Wiley-Interscience,1999.

Polymers useful as pigment dispersants include naturally occurringpolymers, and specific examples thereof include: proteins, such as glue,gelatine, casein, and albumin; naturally occurring rubbers, such as gumarabic and tragacanth; glucosides such as saponin; alginic acid andalginic acid derivatives, such as propylene glycol alginate; andcellulose derivatives, such as methyl cellulose, carboxymethyl celluloseand ethylhydroxy cellulose; wool and silk, and synthetic polymers.

Suitable examples of monomers for synthesizing polymeric dispersantsinclude: acrylic acid, methacrylic acid, maleic acid (or there salts),maleic anhydride, alkyl(meth)acrylates (linear, branched and cycloalkyl)such as methyl(meth)acrylate, n-butyl(meth)acrylate,tert-butyl(meth)acrylate, cyclohexyl(meth)acrylate, and2-ethylhexyl(meth)acrylate; aryl(meth)acrylates such asbenzyl(meth)acrylate, and phenyl(meth)acrylate;hydroxyalkyl(meth)acrylates such as hydroxyethyl(meth)acrylate, andhydroxypropyl(meth)acrylate; (meth)acrylates with other types offunctionalities (e.g. oxiranes, amino, fluoro, polyethylene oxide,phosphate substituted) such as glycidyl (meth)acrylate,dimethylaminoethyl(meth)acrylate, trifluoroethyl acrylate,methoxypolyethyleneglycol (meth)acrylate, and tripropyleneglycol(meth)acrylate phosphate; allyl derivatives such as allyl glycidilether; styrenics such as styrene, 4-methylstyrene, 4-hydroxystyrene,4-acetostyrene, and styrenesulfonic acid; (meth)acrylonitrile;(meth)acrylamides (including N-mono and N,N-disubstituted) such asN-benzyl (meth)acrylamide; maleimides such as N-phenyl maleimide; vinylderivatives such as vinylalcohol, vinylcaprolactam, vinylpyrrolidone,vinylimidazole, vinylnapthalene, and vinyl halides; vinylethers such asvinylmethyl ether; vinylesters of carboxylic acids such as vinylacetate,vinylbutyrate, and vinyl benzoate. Typical condensation type polymersinclude polyurethanes, polyamides, polycarbonates, polyethers,polyureas, polyimines, polyimides, polyketones, polyester, polysiloxane,phenol-formaldehyde, urea-formaldehyde, melamine-formaldehyde,polysulfide, polyacetal or combinations thereof.

Suitable copolymeric dispersants are acrylic acid/acrylonitrilecopolymer, vinyl acetate/acrylic ester copolymer, acrylic acid/acrylicester copolymer, styrene/acrylic acid copolymer, styrene/methacrylicacid copolymer, styrene/methacrylic acid/acrylic ester copolymer,styrene/α-methylstyrene/acrylic acid copolymer,styrene/α-methylstyrene/acrylic acid/acrylic ester copolymer,styrene/maleic acid copolymer, styrene/maleic anhydride copolymer,vinylnaphthalene/acrylic acid copolymer, vinylnapthalene/maleic acidcopolymer, vinyl acetate/ethylene copolymer, vinyl acetate/fattyacid/ethylene copolymer, vinyl acetate/maleic ester copolymer, vinylacetate/crotonic acid copolymer, vinyl acetate/acrylic acid copolymer.

Suitable chemistries of copolymeric dispersants also include:

-   -   Copolymers which are the product of a condensation process of        poly(ethylene imine) with a carboxylic acid terminated polyester        (made by addition polymerization); and    -   Copolymers which are the product of a reaction of        multifunctional isocyanate with a mono-substituted active        H-containing compound like polyester, with a compound containing        two active hydrogens (like a polyether) which serves as a        crosslinker and the residual isocyanates being transformed to        carbamates or urea with compounds containing active hydrogens        and a N-containing ring.

A detailed list of suitable polymeric dispersants is disclosed by MCCUTCHEON, Functional Materials, North American Edition, Glen Rock, N.J.:Manufacturing Confectioner Publishing Co., 1990, pp. 110-129.

Suitable pigment stabilizers are also disclosed in DE (BAYER), U.S. Pat.No. 5,720,802 (XEROX), U.S. Pat. No. 5,713,993 (DU PONT),PCT/GB95/02501, U.S. Pat. No. 5,085,689 (BASF) and U.S. Pat. No.2,303,376 (FUJITSU ISOTEC).

The pigment dispersion can contain one polymeric dispersant or a mixtureof two or more polymeric dispersants to improve the dispersion stabilityfurther. Sometimes surfactants can also be used as pigment dispersants,thus a combination of a polymeric dispersant with a surfactant is alsopossible.

The polymeric dispersant can be non-ionic, anionic or cationic innature; salts of the ionic dispersants can also be used.

The polymeric dispersant preferably has a polymerization degree DPbetween 5 and 1,000, more preferably between 10 and 500 and mostpreferably between 10 and 100.

The polymeric dispersant preferably has a number average molecularweight Mn between 500 and 30,000, more preferably between 1,500 and10,000.

The polymeric dispersant preferably has an average molecular weight Mwsmaller than 100,000, more preferably smaller than 50,000 and mostpreferably smaller than 30,000.

The polymeric dispersant preferably has a polymeric dispersity PDsmaller than 2, more preferably smaller than 1.75 and most preferablysmaller than 1.5.

Commercial examples of polymeric dispersants are the following:

-   -   DISPERBYK™ dispersants available from BYK CHEMIE GMBH;    -   SOLSPERSE™ dispersants available from NOVEON;    -   TEGO™ DISPERS™ dispersants from DEGUSSA;    -   EDAPLAN™ dispersants from MNNZING CHEMIE;    -   ETHACRYL™ dispersants from LYONDELL;    -   GANEX™ dispersants from ISP;    -   DISPEX™ and EFKA™ dispersants from CIBA SPECIALTY CHEMICALS INC;    -   DISPONER™ dispersants from DEUCHEM; and    -   JONCRYL™ dispersants from JOHNSON POLYMER.

Particularly preferred for non-aqueous inkjet inks include Solsperse™dispersants from NOVEON, Efka™ dispersants from CIBA SPECIALTY CHEMICALSINC and Disperbyk™ dispersants from BYK CHEMIE GMBH.

Particularly preferred dispersants for solvent based pigment dispersionsare Solsperse™ 32000 and 39000 from NOVEON.

Particularly preferred dispersants for oil based pigment dispersions areSolsperse™ 11000, 11200, 13940, 16000, 17000 and 19000 from NOVEON.

Particularly preferred dispersants for UV-curable pigment dispersionsare Solsperse™ 32000 and 39000 dispersants from NOVEON.

The polymeric dispersant is preferably used in the pigment dispersion inan amount of 2 to 600 wt %, more preferably 5 to 200 wt % based on theweight of the pigment.

Dispersion Synergists

The non-aqueous inkjet ink according to a preferred embodiment of thepresent invention may contain at least one dispersion synergist. Amixture of dispersion synergists may be used to further improvedispersion stability

The dispersion synergist usually consists of an anionic part and acationic part. The anionic part of the dispersion synergist exhibiting acertain molecular similarity with the color pigment and the cationicpart of the dispersion synergist consists of one or more protons and/orcations to compensate for the charge of the anionic part of thedispersion synergist.

The synergist is preferably added in a smaller amount than the polymericdispersant(s). The ratio of polymeric dispersant/dispersion synergistdepends upon the pigment and should be determined experimentally.Typically, the ratio wt % polymeric dispersant/wt % dispersion synergistis selected between 2:1 to 100:1, preferably between 2:1 and 20:1.

Suitable dispersion synergists that are commercially available includeSolsperse™ 5000 and Solsperse™ 22000 from NOVEON.

A particularly preferred pigment for the magenta ink used in an inkjetink set for manufacturing decorative laminates is adiketopyrrolo-pyrrole pigment. For obtaining excellent dispersionstability and quality, the use of a dispersion synergist was necessaryin the magenta ink. Preferably, a dispersion synergist was used for adiketopyrrolo-pyrrole pigment as those disclosed in EP 1 790 698. Indispersing C.I. Pigment Blue 15, the use of a sulfonatedCu-phthalocyanine dispersion synergist, e.g., Solsperse™ 5000 fromNOVEON is preferred. In a preferred embodiment, the non-aqueous magentaand cyan inkjet inks contain a different dispersion synergist.

Suitable dispersion synergists for yellow non-aqueous inkjet inksinclude those disclosed in EP 1 790 697.

Dispersion Media

The dispersion medium used in the pigmented inkjet ink according to apreferred embodiment of the present invention is a non-aqueous liquid.However, sometimes a small amount, generally less than 10 wt % of waterbased on the total weight dispersion medium, can be present. This wateris not intentionally added but came into the formulation via othercomponents as a contamination, such as, for example polar organicsolvents. Higher amounts of water than 10 wt % of water based on thetotal weight of the dispersion medium tend to make the non-aqueousinkjet inks unstable, preferably the water content is less than 1 wt %based on the total weight dispersion medium and most preferably no waterat all is present.

In a preferred embodiment, the dispersion medium consists of the mixtureof at least two polyalkyleneglycol dialkylethers according to Formula(I).

In another preferred embodiment, the dispersion medium is diluted with aleast one other organic solvent. Suitable organic solvents includealcohols, ketones, esters, ethers, glycols and polyglycols andderivatives thereof, lactones, N-containing solvents such as amides,saturated hydrocarbons and unsaturated hydrocarbons. Preferably,mixtures of one or more of these solvents are used.

In a preferred embodiment, the dispersion medium is diluted with apolyalkyleneglycol derivative selected from the group consisting ofpolyalkyleneglycol monoalkyl ether acetates and polyalkyleneglycolmonoalkyl ethers.

In more preferred embodiment, the polyalkyleneglycol monoalkyl etheracetate is selected from the group consisting of dipropyleneglycolmonomethyl ether acetate and diethyleneglycol monobutyl ether acetate.

In another preferred embodiment, the polyalkyleneglycol monoalkyl etheris selected from the group consisting of triethyleneglycol monobutylether and tripropyleneglycol monomethylether.

In another preferred embodiment, the non-aqueous inkjet ink has theliquid component of the ink consisting of one or more polyalkyleneglycolderivatives and the mixture of polyalkyleneglycol dialkylethers.

Examples of suitable alcohols used to dilute the dispersion mediuminclude methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropylalcohol, n-butyl alcohol, heptyl alcohol, octyl alcohol, cyclohexylalcohol, benzyl alcohol, phenylethyl alcohol, phenylpropyl alcohol,furfuryl alcohol, anise alcohol and fluoroalcohols.

Examples of suitable ketones include acetone, methyl ethyl ketone,methyl n-propyl ketone, methyl isopropyl ketone, methyl n-butyl ketone,methyl isobutyl ketone, methyl n-amyl ketone, methyl isoamyl ketone,diethyl ketone, ethyl n-propyl ketone, ethyl isopropyl ketone, ethyln-butyl ketone, ethyl isobutyl ketone, di-n-propyl ketone, diisobutylketone, cyclohexanone, methylcyclohexanone and isophorone,2,4-pentanedione and hexafluoroacetone.

Examples of suitable esters include methyl acetate, ethyl acetate,n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate,hexyl acetate, octyl acetate, benzyl acetate, phenoxyethyl acetate,ethyl phenyl acetate, methyl lactate, ethyl lactate, propyl lactate,butyl lactate; methyl propionate, ethyl propionate, benzyl propionate,ethylene carbonate, propylene carbonate, amyl acetate, ethyl benzoate,butyl benzoate, butyl laurate, isopropyl myristate, isopropyl palmirate,triethyl phosphate, tributyl phosphate, diethyl phthalate, dibutylphthalate, diethyl malonate, dipropyl malonate, diethyl succinate,dibutyl succinate, diethyl glutarate, diethyl adipate, dibutyl adipateand diethyl sebacate.

Examples of suitable ethers include butyl phenyl ether, benzyl ethylether, hexyl ether, diethyl ether, dipropyl ether, tetrahydrofuran anddioxane.

Examples of suitable glycols and polyglycols include ethylene glycol,diethylene glycol, triethylene glycol, propylene glycol, dipropyleneglycol and tripropylene glycol.

Examples of suitable glycol and polyglycol derivatives include etherssuch as alkylene glycol mono alkyl ethers and polyalkylene glycol monoalkyl ethers and esters such as alkylene glycol mono alkyl esters,polyalkylene glycol mono alkyl esters and polyalkylene glycol dialkylesters. Also, mixed ether/ester compounds are suitable.

Examples of suitable alkylene glycol mono alkyl ethers include ethyleneglycol mono methyl ether, ethylene glycol mono ethyl ether, ethyleneglycol mono propyl ether, ethylene glycol mono butyl ether, ethyleneglycol mono hexyl ether, ethylene glycol mono 2-ethyl-hexyl ether,ethylene glycol mono phenyl ether, propoylene glycol mono methyl ether,propylene glycol mono ethyl ether, propylene glycol mono n-propyl ether,propylene glycol mono n-butyl ether, propylene glycol mono iso-butylether, propylene glycol mono t-butyl ether and propylene glycol monophenyl ether.

Examples of suitable alkylene glycol dialkyl ethers include ethyleneglycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycolmethyl ethyl ether, ethylene glycol dibutyl ether, propylene glycoldimethyl ether, propylene glycol diethyl ether and propylene glycoldibutyl ether.

Examples of suitable polyalkylene glycol mono alkyl ethers includediethylene glycol mono methyl ether, diethylene glycol mono ethyl ether,diethylene glycol mono-n-propyl ether, diethylene glycol mono n-butylether, diethylene glycol mono hexyl ether, triethylene glycol monomethyl ether, triethylene mono ethyl ether, triethylene glycol monobutyl ether, dipropylene mono methyl ether, dipropylene glycol monoethyl ether, dipropylene glycol n-propyl ether, dipropylene glycol monon-butyl ether, dipropylene mono t-butyl ether, tripropylene glycol monomethyl ether, tripropylene glycol mono ethyl ether, tripropylene glycolmono n-propyl ether and tripropylene glycol mono n-butyl ether.

Examples of suitable polyalkylene glycol dialkyl ethers includediethylene glycol dimethyl ether, triethylene glycol dimethyl ether,diethylene glycol diethyl ether, triethylene glycol diethyl ether,diethylene glycol methyl ethyl ether, triethylene glycol methyl ethylether, dipropylene glycol dimethyl ether, dipropylene glycol diethylether, dipropylene di n-propyl ether, dipropylene di t-butyl ether,tripropylene glycol dimethyl ether and tripropylene glycol diethylether.

Examples of suitable glycol esters include ethylene glycol monomethylether acetate, ethylene glycol monoethyl ether acetate, ethylene glycolmonopropyl ether acetate, ethylene glycol monobutyl ether acetate,diethylene glycol monoethyl ether acetate, diethylene glycol monobutylether acetate, propylene glycol monomethyl ether acetate, propyleneglycol monoethyl ether acetate, dipropylene glycol monomethyl etheracetate and propylene glycol monomethyl ether propionate.

Suitable commercial glycol ether solvents include Cellosolve™ solventsand Carbitol™ solvents from UNION CARBIDE, Ektasolve™ solvents fromEASTMAN, Dowanol™ solvents from DOW, Oxitoll™ solvents, Dioxitoll™solvents, Proxitoll™ solvents and Diproxitoll™ solvents from SHELLCHEMICAL and Arcosolv™ solvents from LYONDELL.

Lactones are compounds having a ring structure formed by ester bonds andcan be of the γ-lactone (5-membered ring structure), δ-lactone(6-membered ring structure) or ε-lactone (7-membered ring structure)types. Suitable examples of lactones include γ-butyrolactone,γ-valerolactone, γ-hexalactone, γ-heptalactone, γ-octalactone,γ-nonalactone, γ-decalactone, γ-undecalactone, δ-valerolactone,δ-hexalactone, δ-heptalactone, δ-octalactone, δ-nonalactone,δ-decalactone, δ-undecalactone and ε-caprolactone.

Suitable examples of N-containing organic solvents include2-pyrrolidone, N-methylpyrrolidone, N,N-dimethylacetamid,N,N-dimethylformamid, acetonitril and N,N-dimethyldodecanamide.

Examples of suitable hydrocarbons include saturated hydrocarbons such asn-hexane, isohexane, n-nonane, isononane, dodecane and isododecane;unsaturated hydrocarbons such as 1-hexene, 1-heptene and 1-octene;cyclic saturated hydrocarbons such as cyclohexane, cycloheptane,cyclooctane, cyclodecane and decalin; cyclic unsaturated hydrocarbonssuch as cyclohexene, cycloheptene, cyclooctene,1,1,3,5,7-cyclooctatetraene; and cyclododecene; and aromatichydrocarbons such as benzene, toluene and xylene.

In another preferred embodiment, the dispersion medium includes oiltypes of liquids, alone or in combination with organic solvent(s).

Suitable organic solvents include alcohols, ketones, esters, ethers,glycols and polyglycols and derivatives thereof, lactones, N-containingsolvents such as amides, higher fatty acid ester and mixtures of one ormore of the solvents as described above for solvent based dispersionmedia.

The amount of polar solvent is preferably lower than the amount of oil.The organic solvent preferably has a high boiling point, preferablyabove 200° C. Examples of suitable combinations are disclosed by EP0808347 (XAAR TECHNOLOGY LTD) especially for the use of oleyl alcoholand EP 1157070 (VIDEOJET TECHNOLOGIES INC) for the combination of oiland volatile organic solvent.

Suitable oils include saturated hydrocarbons and unsaturatedhydrocarbons, aromatic oils, paraffinic oils, extracted paraffinic oils,napthenic oils, extracted napthenic oils, hydrotreated light or heavyoils, vegetable oils, white oils, petroleum naptha oils,halogen-substituted hydrocarbons, silicones and derivatives and mixturesthereof.

Hydrocarbons may be selected from straight chain or branched chainaliphatic hydrocarbons, alicyclic hydrocarbons and aromatichydrocarbons. Examples of hydrocarbons are saturated hydrocarbons suchas n-hexane, isohexane, n-nonane, isononane, dodecane and isododecane;unsaturated hydrocarbons such as 1-hexene, 1-heptene and 1-octene;cyclic saturated hydrocarbons such as cyclohexane, cycloheptane,cyclooctane, cyclodecane and decalin; cyclic unsaturated hydrocarbonssuch as cyclohexene, cycloheptene, cyclooctene,1,1,3,5,7-cyclooctatetraene; and cyclododecene; and aromatichydrocarbons such as benzene, toluene, xylene, napthalene, phenanthrene,anthracene and derivatives thereof. In literature the term paraffinicoil is often used. Suitable paraffinic oils can be normal paraffin type(octane and higher alkanes), isoparaffins (isooctane and higheriso-alkanes) and cycloparaffins (cyclooctane and higher cycloalkanes)and mixtures of paraffin oils. The term “liquid paraffin” is often usedto refer to a mixture of mainly including three components of a normalparaffin, an isoparaffin and a monocyclic paraffin, which is obtained byhighly refining a relatively volatile lubricating oil fraction through asulphuric-acid washing or the like, as described in U.S. Pat. No.6,730,153 (SAKATA INX CORP.). Suitable hydrocarbons are also describedas de-aromatized petroleum distillates.

Suitable examples of halogenated hydrocarbons include methylenedichloride, chloroform, carbon tetrachloromethane and methyl chloroform.Other suitable examples of halogen-substituted hydrocarbons includeperfluoro-alkanes, fluorine-based inert liquids and fluorocarboniodides.

Suitable examples of silicone oils include dialklyl polysiloxane (e.g.,hexanemethyl disiloxane, tetramethyl disiloxane, octamethyl trisiloxane,hexanemethyl trisiloxane, heptamethyl trisiloxane, decamethyltetrasiloxane, trifluoropropyl heptamethyl trisiloxane, diethyltetramethyl disiloxane), cyclic dialkyl polysiloxane (e.g., hexamethylcyclotrisiloxane, octamethyl cyclotetrasiloxane, tetramethylcyclotetrasiloxane, tetra(trifluoropropyl)tetramethylcyclotetrasiloxane), and methylphenyl silicone oil.

White oils is a term used for white mineral oils, which are highlyrefined mineral oils that consist of saturated aliphatic and alicyclicnon-polar hydrocarbons. White oils are hydrophobic, colorless,tasteless, odorless, and do not change color over time.

Vegetable oils include semi-drying oils such as soybean oil, cotton seedoil, sunflower oil, rape seed oil, mustard oil, sesame oil and corn oil;non-drying oils such as olive oil, peanut oil and tsubaki oil; anddrying oils such as linseed oil and safflower oil, wherein thesevegetable oils can be used alone or as a mixture thereof.

Examples of other suitable oils include petroleum oils, non-drying oilsand semi-drying oils.

Commercially available suitable oils include the aliphatic hydrocarbonstypes such as the Isopar™ range (isoparaffins) and Varsol/Naphtha rangefrom EXXON CHEMICAL, the Soltrol™ range and hydrocarbons from CHEVRONPHILLIPS CHEMICAL, and the Shellsol™ range from SHELL CHEMICALS.

Suitable commercial normal paraffins include the Norpar™ range fromEXXON MOBIL CHEMICAL.

Suitable commercial napthenic hydrocarbons include the Nappar™ rangefrom EXXON MOBIL CHEMICAL.

Suitable commercial de-aromatized petrolemum distillates include theExxsol™ D types from EXXON MOBIL CHEMICAL.

Suitable commercial fluoro-substituted hydrocarbons includefluorocarbons from DAIKIN INDUSTRIES LTD, Chemical Division.

Suitable commercial silicone oils include the silicone fluid ranges fromSHIN-ETSU CHEMICAL, Silicone Division.

Suitable commercial white oils include Witco™ white oils from CROMPTONCORPORATION.

If the non-aqueous inkjet ink is a curable pigment dispersion, thedispersion medium includes one or more monomers and/or oligomers toobtain a liquid dispersion medium. Preferably, the content of organicsolvent is less than 20 wt % based on the total weight of the pigmentedinkjet ink.

Preferred organic solvents include alcohols, aromatic hydrocarbons,ketones, esters, aliphatic hydrocarbons, higher fatty acids, carbitols,cellosolves, higher fatty acid esters. Suitable alcohols include,methanol, ethanol, propanol and 1-butanol, 1-pentanol, 2-butanol,t.-butanol. Suitable aromatic hydrocarbons include toluene, and xylene.Suitable ketones include methyl ethyl ketone, methyl isobutyl ketone,2,4-pentanedione and hexafluoroacetone. Also glycol, glycolethers,N-methylpyrrolidone, N,N-dimethylacetamid, N, N-dimethylformamid may beused.

Suitable monomers and oligomers can be found in Polymer Handbook, Vol.1+2, 4th Edition, edited by J. BRANDRUP, et al., Wiley-Interscience,1999.

Suitable examples of monomers for curable pigmented inkjet inks include:acrylic acid, methacrylic acid, maleic acid (or their salts), maleicanhydride; alkyl(meth)acrylates (linear, branched and cycloalkyl) suchas methyl(meth)acrylate, n-butyl(meth)acrylate,tert-butyl(meth)acrylate, cyclohexyl(meth)acrylate and2-ethylhexyl(meth)acrylate; aryl(meth)acrylates such asbenzyl(meth)acrylate and phenyl(meth)acrylate;hydroxyalkyl(meth)acrylates such as hydroxyethyl(meth)acrylate andhydroxypropyl(meth)acrylate; (meth)acrylates with other types offunctionalities (e.g. oxirane, amino, fluoro, polyethylene oxide,phosphate-substituted) such as glycidyl (meth)acrylate,dimethylaminoethyl(meth)acrylate, trifluoroethyl acrylate,methoxypolyethyleneglycol (meth)acrylate andtripropyleneglycol(meth)acrylate phosphate; allyl derivatives such asallyl glycidyl ether; styrenics such as styrene, 4-methylstyrene,4-hydroxystyrene, and 4-acetoxystyrene; (meth)acrylonitrile;(meth)acrylamides (including N-mono and N,N-disubstituted) such asN-benzyl (meth)acrylamide; maleimides such as N-phenyl maleimide,N-benzyl maleimide and N-ethyl maleimide; vinyl derivatives such asvinylcaprolactam, vinylpyrrolidone, vinylimidazole, vinylnaphthalene andvinyl halides; vinylethers such as vinylmethyl ether; and vinylesters ofcarboxylic acids such as vinylacetate and vinylbutyrate.

A combination of monomers, oligomers and/or prepolymers may also beused. The monomers, oligomers and/or prepolymers may possess differentdegrees of functionality, and a mixture including combinations of mono-,di-, tri-and higher functionality monomers, oligomers and/or prepolymersmay be used.

Binders

The non-aqueous inkjet ink compositions may include a binder resin.However for making decorative laminates, preferably no binder is presentas it would influence negatively the quality and speed of impregnationwith an impregnating resin after inkjet printing.

The binder functions as a viscosity controlling agent and also providesfixability relative to a substrate, e.g., a polyvinyl chloridesubstrate. The binder must be selected to have a good solubility in thesolvent(s).

Suitable examples of binder resins include acrylic resins, modifiedacrylic resins, styrene acrylic resins, acrylic copolymers, acrylateresins, aldehyde resins, rosins, rosin esters, modified rosins andmodified rosin resins, acetyl polymers, acetal resins such as polyvinylbutyral, ketone resins, phenolic resins and modified phenolic resins,maleic resins and modified maleic resins, terpene resins, polyesterresins, polyamide resins, polyurethane resins, epoxy resins, vinylresins, vinyl chloride-vinyl acetate copolymer resins, cellulose typeresins such as nitro cellulose, cellulose acetopropionate and celluloseacetate butyrate, and vinyl toluene-α-methylstylene copolymer resin.These binders may be used alone or in a mixture thereof. The binder ispreferably a film-forming thermoplastic resin.

The amount of binder resin in the inkjet ink is preferably in the rangeof 0.1 to 30 wt %, more preferably 0.3 to 10 wt %, most preferably 0.5to 5 wt % based on the total weight of the inkjet ink.

Surfactants

Decorative paper has an open surface so that it can be rapidly anduniformly impregnated with melamine-formaldehyde resins,urea-formaldehyde resins, phenol-formaldehyde resins and otherimpregnating resins. The non-aqueous inkjet inks according to preferredembodiments of the present invention do not require the presence of asurfactant for printing images of high quality on decorative base paper.However, if the ink receiver consisted of a decorative base paper coatedwith an ink receiving layer, preferably the non-aqueous inkjet inkcontained at least one surfactant for controlling the dot size of an inkdroplet on the ink receiver.

The surfactant(s) can be anionic, cationic, non-ionic, or zwitter-ionicand are usually added in a total quantity less than 20 wt % based on thetotal weight of the pigmented inkjet ink and particularly in a totalless than 10 wt % based on the total weight of the pigmented inkjet ink.

Suitable surfactants for the pigmented inkjet ink include fluorinatedsurfactants, fatty acid salts, ester salts of a higher alcohol,alkylbenzene sulphonate salts, sulphosuccinate ester salts and phosphateester salts of a higher alcohol (for example, sodiumdodecylbenzenesulphonate and sodium dioctylsulphosuccinate), ethyleneoxide adducts of a higher alcohol, ethylene oxide adducts of analkylphenol, ethylene oxide adducts of a polyhydric alcohol fatty acidester, and acetylene glycol and ethylene oxide adducts thereof (forexample, polyoxyethylene nonylphenyl ether, and SURFYNOL™ M 104, 104H,440, 465 and TG available from AIR PRODUCTS & CHEMICALS INC.).

Humectants/Penetrants

Suitable humectants include triacetin, N-methyl-2-pyrrolidone, glycerol,urea, thiourea, ethylene urea, alkyl urea, alkyl thiourea, dialkyl ureaand dialkyl thiourea, diols, including ethanediols, propanediols,propanetriols, butanediols, pentanediols, and hexanediols; glycols,including propylene glycol, polypropylene glycol, ethylene glycol,polyethylene glycol, diethylene glycol, tetraethylene glycol, andmixtures and derivatives thereof. Preferred humectants are triethyleneglycol mono butylether, glycerol and 1,2-hexanediol. Other preferredhumectants include cyclohexane, 2-pyrrolidone, ethylenecarbonate,propyleencarbonate and gamma-butyrolactone. The humectant is preferablyadded to the non-aqueous inkjet ink in an amount of 0.1 to 40 wt %, morepreferably 0.1 to 10 wt %, and most preferably approximately 4.0 to 6.0wt % each based on the total weight of the non-aqueous inkjet ink.

EXAMPLES Materials

All materials used in the examples were readily available from standardsources such as Aldrich Chemical Co. (Belgium) and Acros (Belgium)unless otherwise specified.

PB15 is the abbreviation for C.I. Pigment Blue 15 for which HostapermBlue B4G-KR™ from CLARIANT was used. PY150 is the abbreviation for C.I.Pigment Yellow 150 for which Pigment Yellow E4GN-GT from BAYER was used.PY150B is the abbreviation for C.I. Pigment Yellow 150 for whichChromophtal Yellow™ LA2 from Ciba Specialty Chemicals was used. PR254 isthe abbreviation for C.I. Pigment Red 254 for which Irgazin™ DPP Red BTRfrom Ciba Specialty Chemicals was used. PB7 is the abbreviation for C.I.Pigment Black 7 for which Special Black™ 550 from DEGUSSA was used.Special Black™ 550 has a BET surface area of about 110 m²/g. SPECIALBLACK 550 is a low structured Furnace Black having a BET surface area ofabout 110 m²/g and an average primary particle size of 25 nm. SOLSPERSE™39000 is a hyperdispersant from NOVEON. SOLSPERSE™ 5000 is a dispersionsynergist from NOVEON. DEGDEE is diethyleneglycol diethylether fromACROS. PEGDME250 is a polyethyleneglycol dimethylether with an averagemolecular weight of 250 from CLARIANT sold under the tradename ofPolyglycol DME 250.

PEGDME500 is a polyethyleneglycol dimethylether with an averagemolecular weight of 500 from CLARIANT sold under the tradename ofPolyglycol DME 500.DPGMMEA is dipropyleneglycol monomethyl ether acetate from DOW.DEGMBEA is diethyleneglycol monobutylether from Eastman Kodak.TEGMBE is triethyleneglycol monobutyl ether from WAKO CHEMICALS.TTEGDME is tetraethyleneglycol dimethylether from ALDRICH.PGMPhE is propyleneglycol monophenylether from DOW.TPGMME is tripropyleneglycol monomethylether from ALDRICH.

Measurement Methods 1. Average Particle Size

The average particle size diameter was determined with a BrookhavenInstruments Particle Sizer BI90plus based upon the principle of dynamiclight scattering. The ink or dispersion was diluted with ethyl acetateto a pigment concentration of 0.002 wt %. The measurement settings ofthe BI90plus were: 5 runs at 23° C., angle of 90°, wavelength of 635 nmand graphics=correction function.

2. Pigment Dispersion Stability

The pigment dispersion stability was determined by comparing the averageparticle size of the pigments in the dispersion or the ink with theaverage particle size of the pigments of the same ink subjected to aheat treatment of 7 days at 83° C. in a sealed container. The % growthbased on the original average particle size was used as a parameter toevaluate the pigment dispersion stability. The smaller the % growthvalue, the more stable the pigment dispersion was. The % growth valueshould preferably be less than 40%, more preferably less than 25% andmost preferably less than 10%. For preventing the clogging of thenozzles, the average particle size should also stay below 200 nm,preferably below 150 nm.

3. Viscosity

The viscosity of the inkjet inks was measured using a Brookfield DV-II+viscometer at 25° C. and shear rate of 15 RPM.

4. Surface Tension

The surface tension of the inkjet inks was measured with a KRÜSStensiometer K9 at 25° C. after 60 seconds.

5. Optical Density

The optical density of single color print patches was measured using aGretag SPM50.

6. Cielab Values

Printed samples were measured with a spectrophotometer (Gretag SPM50) todetermine the coordinates of the L*a*b* colors system of the colordifference indication method specified in CIE (Commission Internationalde l'Eclairage). In this case, the measurement was carried out underconditions of light source D50, provision of no light source filter,absolute white as reference white, and angle of visibility 2°.

7. Latency Time

The latency time was determined by performing a nozzle check of theinkjet ink on the Agfa :Dotrix printer at the start and after idletimes. During the idle time the print heads were at rest without anymaintenance and without capping of the print heads. The latency time wasthe time interval up to which all nozzles performed well in the nozzlecheck after the idle time.

Example 1

This example illustrates that the use of polyalkyleneglycoldialkylethers with a molecular weight larger than 250 improves thepigment dispersion quality and stability compared to lower molecularweight polyalkyleneglycol dialkylethers.

Preparation and Evaluation of Inkjet Inks

All inkjet inks were prepared in the same manner to obtain a compositionas described in Table 1 and Table 2, except that the concentration ofthe dispersion synergist and the type of solvent (the “dispersionsolvent”) in the milling mixture were altered. The concentration of thedispersion solvent in the milling mixture was compensated in function ofthe amount of dispersion synergist.

A milling mixture with 15 wt % pigment and 15 wt % dispersant wasprepared by adding the pigment PB15:4, the polymeric dispersantSolsperse ^(M) 39000 and the dispersant synergist Solsperse ^(M) 5000 tothe dispersion solvent. The milling mixture was then milled duringcooling by a NETZSCH™ LABSTAR1 at a 50% volume filling withyttrium-stabilized zirconium oxide-beads of 0.4 mm diameter (“high wearresistant zirconia grinding media” from TOSOH Co.) and a residence timeof 45 minutes.

The inventive non-aqueous inkjet inks INV-1 to INV-7 and the comparativenon-aqueous inkjet inks COMP-1 to COMP-3 were then prepared according toTable 1 and Table 2 by adding 65 parts by weight of a solvent (the “inksolvent”) to 35 parts by weight of the milling mixture during stirringat room temperature.

TABLE 1 wt % of COMP- COMP- COMP- compound: INV-1 1 INV-2 2 INV-3 3 PB155.250 5.250 5.250 5.250 5.250 5.250 Solsperse ™ 5.250 5.250 5.250 5.2505.250 5.250 39000 Solsperse ™ 0.350 0.350 0.175 0.175 0.088 0.088 5000Dispersion solvent DEGDEE 24.150  24.150  24.325  24.325  24.412 24.412  PEGDME250 — — — — — — Ink solvent DEGDEE — 65.000  — 65.000  —65.000  PEGDME250 65.000  — 65.000  — 65.000  —

TABLE 2 wt % of compound: INV-4 INV-5 INV-6 INV-7 PB15 5.250 5.250 5.2505.250 Solsperse ™ 39000 5.250 5.250 5.250 5.250 Solsperse ™ 5000 0.1750.175 0.088 0.088 Dispersion solvent DEGDEE — — — — PEGDME250 24.32524.325 24.412 24.412 Ink solvent DEGDEE — 65.000 — 65.000 PEGDME25065.000 — 65.000 —

The commercial products PEGDME 250 and PEGDME 500 available fromCLARIANT are a mixture of polyethyleneglycol dimethylethers. Thecomposition of the mixtures of polyethyleneglycol dimethylethers, PEGDME250 and PEGDME 500, was analyzed by gas chromatography. The GC analysiswas performed using an AGILENT Technologies™ type 6890 with a FIDdetector (flame ionization detector). The liquid mixture was dilutedwith methylene chloride and 1 p1 of this dliution was injected. Thecolumn used was a J&W DB1 column (capillary column type) having a 30meter length, an inside diameter of 0.25 meter and a film thickness of0.25 μm. The stationary phase was polysiloxane polymer, the mobile phasewas He gas, with a flow rate of 2 ml/minute. The temperature gradientwas the following: start at 60° C., then raise the temperature by 15°C./min up to 320° C. and keep for 15 minutes at 320° C. The analyticalresults for PEGDME250 and PEGDME500 are given in Table 3.

Polyethyleneglycol dimethylether can be represented by Formula (A):

wherein n represents an integer.

TABLE 3 wt % of polyethyleneglycol dimethylether with PEGDME250PEGDME500 MW n = 2 0 0 118 n = 3 5 0 162 n = 4 13 0 206 n = 5 20 1 250 n= 6 22 3 294 n = 7 18 9 338 n = 8 11 13 382 n = 9 6 13 426 n = 10 3 14470 n = 11 1 13 514 n = 12 1 11 558 n = 13 0 9 602 n = 14 0 7 646 n = 150 4 690 n = 16 0 2 734 n = 17 0 1 778

The dispersion stability was evaluated by comparing the average particlesize measured after preparation of the ink and the average particle sizemeasured on the ink after a heat treatment of 7 days at 83° C. Theresults are given in Table 4.

TABLE 4 Average particle size Non- after 7 aqueous after ink days atinkjet ink preparation 83° C. % growth INV-1 126 nm 142 nm 12% COMP-1120 nm 142 nm 17% INV-2 125 nm 157 nm 24% COMP-2 126 nm 167 nm 28% INV-3137 nm 169 nm 20% COMP-3 147 nm 193 nm 31% INV-4 109 nm 104 nm 0% INV-5107 nm 104 nm 0% INV-6 109 nm 109 nm 0% INV-7 104 nm 102 nm 0%

From Table 4, it should be clear that the use of polyethyleneglycoldimethylethers (PEGDME250) with a molecular weight larger than 250instead of the diethyleneglycol diethylether (DEGDEE) with a molecularweight of 118 delivered more stable non-aqueous inkjet inks. Theinventive inkjet inks INV-4 to INV-7 show that the use ofpolyethyleneglycol dimethylethers with a molecular weight larger than250 as dispersion solvents resulted in inkjet inks of superior qualityand stability.

Example 2

This example illustrates that polyalkyleneglycol dialkylethers with amolecular weight larger than 250 as dispersion solvents in the millingmixture allows a wider choice of ink solvents.

Preparation and Evaluation of Inkjet Inks

All inkjet inks were prepared in the same manner to obtain a compositionas described in Table 5 and Table 6, except that the concentration ofthe dispersion synergist and the type of solvent (the “dispersionsolvent”) in the milling mixture were altered.

A milling mixture with 15 wt % pigment and 15 wt % dispersant wasprepared by adding the pigment PY150 and the polymeric dispersantSolsperse™ 39000 to the dispersion solvent. The milling mixture was thenmilled during cooling by a NETZSCH™ LABSTAR1 at a 50% volume fillingwith yttrium-stabilized zirconium oxide-beads of 0.4 mm diameter (“highwear resistant zirconia grinding media” from TOSOH Co.) and a residencetime of 45 minutes.

The comparative non-aqueous inkjet inks COMP-4 to COMP-9 were thenprepared according to Table 5 and the inventive non-aqueous inkjet inksINV-8 to INV-13 were then prepared according to Table 6 by adding 65parts by weight of a solvent (the “ink solvent”) to 35 parts by weightof the milling mixture during stirring at room temperature. On dilutingthe milling mixture according to inventive non-aqueous inkjet ink INV-8with 65 parts of water instead of DEGDEE, a precipitated andinhomogeneous slurry was obtained.

TABLE 5 wt % of COMP- COMP- COMP- COMP- COMP- compound: 4 5 6 7 8 COMP-9PY150 5.25 5.25 5.25 5.25 5.25 5.25 Solsperse ™ 5.25 5.25 5.25 5.25 5.255.25 39000 Dispersion solvent DEGDEE 24.50  24.50  24.50  24.50  24.50 24.50  Ink solvent DEGDEE 65.00  — — — — — DPGMMEA — 65.00  — — — —TEGMBE — — 65.00  — — — PGMPhE — — — 65.00  — — TPGMME — — — — 65.00  —TTEGDME — — — — — 65.00 

TABLE 6 wt % of compound: INV-8 INV-9 INV-10 INV-11 INV-12 INV-13 PY1505.25 5.25 5.25 5.25 5.25 5.25 Solsperse ™ 5.25 5.25 5.25 5.25 5.25 5.2539000 Dispersion solvent PEGDME250 24.50  24.50  24.50  24.50  24.50 24.50  Ink solvent DEGDEE 65.00  — — — — — PEGDME250 — 65.00  — — — —DPGMMEA — — 65.00  — — — TEGMBE — — — 65.00  — — PGMPhE — — — — 65.00  —TPGMME — — — — — 65.00 

The dispersion stability was evaluated by comparing the average particlesize measured after preparation of the ink and the average particle sizemeasured in the ink after a heat treatment of 7 days at 83° C. Theresults are given in Table 7.

TABLE 7 Average particle size after 7 Non-aqueous after days at inkjetink preparation 83° C. % growth COMP-4 127 nm 1247 nm 882% COMP-5 124 nm788 nm 535% COMP-6 111 nm 613 nm 452% COMP-7 104 nm 170 nm 63% COMP-8122 nm 213 nm 74% COMP-9 107 nm 343 nm 220% INV-8  96 nm  95 nm 0% INV-9 95 nm 111 nm 17% INV-10  93 nm  92 nm 0% INV-11  94 nm 126 nm 34%INV-12  95 nm 105 nm 10% INV-13  91 nm 108 nm 19%

In Table 7, it can be seen that the inventive inkjet inks INV-8 toINV-13 using polyethyleneglycol dimethylethers with a molecular weightlarger than 250 as the dispersion solvent were much more stable inaverage particle size than the comparative non-aqueous inkjet inksCOMP-4 to COMP-9 having DEGDEE as the dispersion solvent. Hence, a widerchoice of ink solvents was available to adjust the ink for viscosity andjetting performance. Moreover, the average pigment particle size in theinventive inkjet inks INV-8 to INV-13 was smaller than in thecomparative non-aqueous inkjet inks COMP-4 to COMP-9, which isadvantageous for preventing nozzle clogging and for color strength. Thecomparative non-aqueous inkjet inks COMP-4 and COMP-9 show that usingonly lower molecular weight polyethyleneglycol dimethylethers(diethyleneglycol dimethylether and tetraethyleneglycol dimethylether)for the dispersion and ink solvents led to poor dispersion quality andstability.

Example 3

This example illustrates a CMYK non-aqueous inkjet ink set suitable forproducing decorative laminates with a warm wooden color appearance.

Preparation and Evaluation of Inkjet Inks

All non-aqueous inkjet inks were prepared in the same manner to obtain acomposition as described in Table 8. If a dispersion synergist waspresent, the concentration of the dispersion solvent in the millingmixture was compensated for by the function of the dispersion synergist.

A milling mixture with 15 wt % pigment and 15 wt % dispersant wasprepared by adding the pigment, the polymeric dispersant Solsperse™39000 and, optionally, the dispersant synergist to the dispersionsolvent. The milling mixture was then milled during cooling by aNETZSCH™ LABSTAR1 at a 50% volume filling with yttrium-stabilizedzirconium oxide-beads of 0.4 mm diameter (“high wear resistant zirconiagrinding media” from TOSOH Co.) and a residence time of 45 minutes.

The cyan, magenta and yellow non-aqueous inkjet inks were then preparedby adding 60 parts by weight of DEGMBEA and 5 parts by weight ofPEGDME500 to 35 parts by weight of the milling mixture during stirringat room temperature. The black non-aqueous inkjet ink was prepared byadding 57 parts by weight of DEGMBEA and 10 parts by weight of PEGDME500to 33 parts by weight of the milling mixture during stirring at roomtemperature.

TABLE 8 Non-aqueous CMYK inkjet ink set Cyan Magenta Yellow Black In wt% of the ink ink ink ink ink PB15 5.25 — — — PR254 — 5.25 — — PY150 — —5.25 — PB7 — — — 5.00 Solsperse ™ 39000 5.25 5.25 5.25 5.00 Solsperse ™5000 0.35 — — — SYN-1 — 0.35 — — Dispersion solvent PEGDME 500 24.1524.15 24.50 23.30 Ink solvent DEGMBEA 60.00 60.00 60.00 56.70 PEGDME 5005.00 5.00 5.00 10.00

The dispersion synergist SYN-1 was used for preparing the magenta inkjetink. A suitable synthesis method for the dispersion synergist SYN-1 canbe found in EP 1 790 698.

Table 9 shows that the non-aqueous inkjet ink set according to Table 8exhibited excellent ink characteristics and dispersion stability makingit a suitable inkjet ink set for the single pass inkjet printer :DOTRIX™from AGFA.

TABLE 9 Cyan Magenta Yellow Black ink ink ink ink Ink characteristicsViscosity (mPa · s) (25° C.) 10.2 10.5 11.3 10.1 surface tension (mN/m)31.25 31.25 31.25 31.25 (25° C.) Dispersion stability of inks Averageparticle size 108 nm 125 nm 155 nm 96 nm after preparation Averageparticle size 107 nm 123 nm 155 nm 97 nm after 7 days at 83° C. % growthin average 0% 0%   0%   1% particle size Viscosity after 10.2 10.5 11.310.1 preparation (mPas) Viscosity after 7 days at 10.2 10.6 10.7 10.083° C. (mPa · s) % change in viscosity 0% 1% −5% −1%

The excellent pigment dispersion stability is not only demonstrated bythe average particle size remaining unchanged after a heat treatment forall four inks, but also by the stable viscosity. A large change inviscosity generally leads to jetting problems and/or deterioratedjetting quality because the creation of an ink droplet by an inkjetprint head is largely influenced by ink viscosity.

Each of the inks of the CMYK ink set was degassed prior to jetting withthe Agfa :Dotrix™ single pass inkjet printer equipped with Toshiba TECCB1 printheads. These piezoelectric drop-on-demand printheads arecapable of jetting multi-drops within one dot (8 levels) with a minimumof 6 picoliters to maximum 42 picoliters per dot. The standard frequencyused was 4.8 KHz/dot (7 drops) and the driving voltage was 22 Volts(ejection orifice diameter=26 microns). The order of printing of thedifferent inks at 300 dpi was first cyan, then magenta, yellow andblack.

A series of printing experiments were performed on an uncoated whitedecorative base paper of 80 g/m² with a Bekk smoothness of 100-200seconds and containing 32-40% of a titanium dioxide pigment and on twosimilar decorative base papers coated with an ink-receiving layer.

A first printing experiment was performed on an uncoated decor paper of80 g/m². The results for the optical density and the L*a*b*-values aregiven in Table 10.

TABLE 10 Ink(s) printed on uncoated Optical paper Density L* a* b* None0.09 96.3 0.3 3.8 C 0.70 67.6 −22.0 −32.9 M 0.64 68.6 47.4 13.2 Y 0.6091.5 −4.4 49.3 K 0.61 57.0 −0.7 −0.4 Y + M 0.55 71.4 39.7 20.0 C + Y0.61 69.9 −33.2 1.3 C + M 0.62 60.7 −3.6 −16.2 C + M + K 0.49 64.7 −9.5−1.8

A second printing experiment was performed on a coated decor paperARJOJET from ARJO WIGGINS. The results for the optical density and theL*a*b*-values are given in Table 11.

TABLE 11 Ink(s) printed on Optical coated paper Density L* a* b* None0.08 97.0 0.8 3.9 C 0.94 57.5 −19.9 −43.4 M 0.93 61.1 60.8 29.0 Y 0.8790.4 −3.5 68.0 K 0.95 40.1 0.3 0.3 Y + M 0.97 60.0 60.0 39.0 C + Y 1.0453.0 −43.1 −3.3 C + M 1.03 40.7 −2.5 −19.0 C + M + Y 1.03 42.9 −10.8−13.6

A third printing experiment was performed on a coated decor papersuitable for inkjet from Technocell Dekor. The results for the opticaldensity and the L*a*b*-values are given in Table 12.

TABLE 12 Ink(s) printed on Optical coated paper Density L* a* b* None0.07 98.5 0.2 4.6 C 0.85 58.0 −16.1 −40.0 M 0.86 61.7 58.0 26.9 Y 0.8790.8 −1.4 69.6 K 0.80 46.7 0.1 0.8 Y + M 1.20 59.0 59.2 48.7 C + Y 1.0451.2 −34.9 14.1 C + M 1.06 35.3 9.2 −13.6 C + M + Y 1.11 33.8 −0.7 −2.2

The results in Table 10, Table 11 and Table 12 show that high opticaldensities were obtained. The highest optical densities were obtainedwhen printing on coated decor paper. The L*a*b*-values illustrate that adesired wide range of color gamut values for the ink set was obtained.

A wood-imitation image and a commercial logo was printed with the singlepass inkjet printer :DOTRIX™ from AGFA on the classic decorative basepaper substrate ARJOJET from ARJO WIGGINS. The decorative paper wasimpregnated with a melamine-formaldehyde resin and integrated into adecorative laminate. A floor made with the decorative laminate had thedesired warm color of wood.

The jetting performance of this ink set was further tested bydetermining the latency time for this ink set in the :Dotrix printer. Alatency time of at least 116 hours for all four inks was found, which isconsidered to be a very long latency time for a solvent based inkjetink.

Example 4

This example illustrates that small amounts of water can be tolerated byinkjet inks in accordance with preferred embodiments of the presentinvention.

Preparation and Evaluation of Inkjet Inks

The inkjet inks in this example were prepared in the same manner asdescribed for EXAMPLE 2.

A series of yellow inks was prepared according to Table 13 havingincreasing amounts of water.

TABLE 13 Wt % of compound Yellow-1 Yellow-2 Yellow-3 Yellow-4 PY150 5.255.25 5.25 5.25 Solsperse ™ 39000 5.25 5.25 5.25 5.25 Dispersion solventPEGDME 500 24.5 24.5 24.5 24.5 Ink solvent DEGMBEA 64.0 62.0 60.0 55.0water 1.0 3.0 5.0 10.0

A series of cyan inks was prepared according to Table 14 havingincreasing amounts of water.

TABLE 14 Wt % of compound Cyan-1 Cyan-2 Cyan-3 Cyan-4 PB15 5.25 5.255.25 5.25 Solsperse ™ 39000 5.25 5.25 5.25 5.25 Solsperse ™ 5000 0.350.35 0.35 0.35 Dispersion solvent PEGDME 500 24.15 24.15 24.15 24.15 Inksolvent DEGMBEA 64.0 62.0 60.0 55.0 Water 1.0 3.0 5.0 10.0

A series of black inks was prepared according to Table having increasingamounts of water.

TABLE 15 Wt % of compound Black-1 Black-2 Black-3 Black-4 PB7 5.00 5.005.00 5.00 Solsperse ™ 39000 5.00 5.00 5.00 5.00 Dispersion solventPEGDME 500 23.30 23.30 23.30 23.30 Ink solvent DEGMBEA 60.70 58.70 56.7051.70 PEGDME 500 5.0 5.0 5.0 5.0 Water 1.0 3.0 5.0 10.0

The effect of the amount of water in these inks was evaluated by theeffect on the viscosity after preparation and after a heat treatment of1 week at 83° C. The results are given in Table 16.

TABLE 16 Viscosity Viscosity after after preparation 1 week at 83° C.Inkjet ink (in mPa · s) (in mPa · s) Jettability Yellow-1 10.7 10.2 OKYellow-2 11.5 11.9 OK Yellow-3 87.2 29.5 Not jettable Yellow-4 90.3170.1 Not jettable Cyan-1 11.2 10.3 OK Cyan-2 11.7 11.5 OK Cyan-3 14.015.5 Deteriorated Cyan-4 16.8 17.7 Deteriorated Black-1 10.6 10.7 OKBlack-2 11.2 11.5 OK Black-3 12.1 12.7 OK Black-4 11.6 16.6 Deteriorated

The results in Table 16 show that some water may be present in thenon-aqueous inkjet inks of a preferred embodiment of the presentinvention. Increasing the amount of water in these inks give higher andless stable ink viscosities. At a certain amount of water, the viscosityof the ink became too high for jetting the ink using the same jettingconditions. The tolerable amount of water was dependent upon thespecific ink. Generally, not more than 10 wt % of water based upon theink can be tolerated as illustrated by the ink Black-4, but it can belower as can be seen for the yellow inks (3 wt %).

Example 5

This example illustrates that the inkjet inks of a preferred embodimentof the present invention with high pigment concentrations exhibit thesame excellent dispersion stability as typical inkjet inks with lowerpigment concentrations of 1 to 6 wt %. Inkjet inks with high pigmentconcentrations have been investigated in the past for improving thedrying characteristics and the printing speed, but always poordispersion stability was obtained.

Preparation and Evaluation of Inkjet Inks

The inkjet inks in this example were prepared in the same manner asdescribed for EXAMPLE 2.

A series of yellow inks with higher pigment loads was prepared accordingto Table 17.

TABLE 17 Wt % of compound Yellow-5 Yellow-6 Yellow-7 PY150 5.25 7.8810.50 Solsperse ™ 39000 5.25 7.88 10.50 Dispersion solvent PEGDME 50024.50 36.74 49.00 Ink solvent DEGMBEA 65.00 47.50 30.00

A series of cyan inks with higher pigment loads was prepared accordingto Table 18.

TABLE 18 Wt % of compound Cyan-5 Cyan-6 Cyan-7 PB15 5.25 7.88 10.50Solsperse ™ 39000 5.25 7.88 10.50 Solsperse ™ 5000 0.35 0.525 0.70Dispersion solvent PEGDME 500 24.15 36.215 48.30 Ink solvent DEGMBEA65.0 47.5 30.0

A series of black inks with higher pigment loads was prepared accordingto Table 19.

TABLE 19 Wt % of compound Black-5 Black-6 Black-7 PB7 5.00 7.50 10.00Solsperse ™ 39000 5.00 7.50 10.00 Dispersion solvent PEGDME 500 23.3035.0 46.6 Ink solvent DEGMBEA 61.7 45.0 28.4 PEGDME 500 5.0 5.0 5.0

The pigment dispersion stability of these inkjet inks was evaluated bymeasuring the average particle size before and after a heat treatment of7 days at 83° C. The results are given in Table 20.

TABLE 20 Average particle size Non-aqueous After After 7 days inkjet inkpreparation at 83° C. % growth Yellow-5 99 nm  90 nm 0% Yellow-6 96 nm 99 nm 3% Yellow-7 97 nm 101 nm 4% Cyan-5 112 nm  112 nm 0% Cyan-6 111nm  111 nm 0% Cyan-7 112 nm  110 nm 0% Black-5 90 nm  89 nm 0% Black-692 nm  91 nm 0% Black-7 89 nm  90 nm 1%

From Table 20 it can be seen that the average particle size after a heattreatment remains practically unchanged even for inks having pigmentconcentrations higher than 10 wt % based upon the total ink. Thesehighly concentrated solvent inkjet inks have the advantage that reducedamounts of solvent are jetted onto the substrates, which solvents needto be absorbed and/or evaporated.

While preferred embodiments of the present invention have been describedabove, it is to be understood that variations and modifications will beapparent to those skilled in the art without departing the scope andspirit of the present invention. The scope of the present invention,therefore, is to be determined solely by the following claims.

1-13. (canceled)
 14. A non-aqueous inkjet ink set for single pass inkjetprinting including a non aqueous inkjet ink comprising: adiketopyrrolo-pyrrole pigment; a dispersion synergist; a polymericdispersant; and at least one polyalkyleneglycol dialkylether having amolecular weight of at least 250; wherein the polyalkyleneglycoldialkylether is represented by Formula (I):

R₁ and R₂ are each independently selected from an alkyl group having 1to 4 carbon atoms; Y represents an ethylene group or a propylene group;n is an integer selected from 5 to 20; and the diketopyrrolo-pyrrolepigment has an average particle size diameter of less than 200 nm asmeasured by dynamic light scattering at a wavelength of 635 nm.
 15. Thenon-aqueous inkjet ink set according to claim 14, wherein thediketopyrrolo-pyrrole pigment is C.I. Pigment Red
 254. 16. Thenon-aqueous inkjet ink set according to claim 14, further comprising anon-aqueous black inkjet ink including the at least onepolyalkyleneglycol dialkylether.
 17. The non-aqueous inkjet ink setaccording to claim 16, wherein the non-aqueous black inkjet ink includesa carbon black pigment with a BET surface area smaller than 200 m²/gaccording to ASTM D6556-04.
 18. The non-aqueous inkjet ink set accordingto claim 14, further comprising a non-aqueous yellow inkjet inkincluding C.I. Pigment Yellow 150 and the at least onepolyalkyleneglycol dialkylether.
 19. The non-aqueous inkjet ink setaccording to claim 18, wherein the C.I. Pigment Yellow 150 has anaverage particle size diameter of less than 200 nm as measured bydynamic light scattering at a wavelength of 635 nm.
 20. The non-aqueousinkjet ink set according to claim 14, further comprising a non-aqueouscyan inkjet ink including C.I. Pigment Blue 15:3 or C.I. Pigment Blue15:4 and the at least one polyalkyleneglycol dialkylether.
 21. Thenon-aqueous inkjet ink set according to claim 14, wherein at least onenon-aqueous inkjet ink includes a pigment and a mixture of at least twopolyalkyleneglycol dialkylethers having four or more alkyleneglycolgroups, wherein the number of alkyleneglycol groups is not the same inthe two polyalkyleneglycol dialkylethers.
 22. The non-aqueous inkjet inkset according to claim 14, wherein R₁ and R₂ represent methyl.
 23. Thenon-aqueous inkjet ink set according to claim 14, wherein Y representsan ethylene group.
 24. The non-aqueous inkjet ink set according to claim14, wherein at least one non-aqueous inkjet ink includes apolyalkyleneglycol derivative selected from the group consisting ofpolyalkyleneglycol monoalkyl ether acetates and polyalkyleneglycolmonoalkyl ethers.
 25. The non-aqueous inkjet ink set according to claim24, wherein the polyalkyleneglycol derivative is selected from the groupconsisting of dipropyleneglycol monomethyl ether acetate,diethyleneglycol monobutyl ether acetate, triethyleneglycol monobutylether, and tripropyleneglycol monomethylether.
 26. A method formanufacturing decorative laminates comprising the steps: a) providing adecorative paper; b) inkjet printing on the decorative paper with anon-aqueous inkjet ink set as defined by claim 14; and c) impregnatingthe printed decorative paper with an impregnating resin.
 27. The methodaccording to claim 26, wherein the step b) is performed by single passinkjet printing.
 28. A method for preparing the non-aqueous inkjet inkset as defined by claim 14, wherein the at least one polyalkyleneglycoldialkylether having a molecular weight of at least 250 is used as adispersion solvent.